Oxadiazolinone derivative and its production and use

ABSTRACT

The present invention relates to an oxadiazolinone derivative represented by the following general formula, a process for producing the same and insecticides containing the same as an active ingredient: ##STR1## wherein R 1  is a haloalkyl group or a haloalkoxy group; R 2  is a halogen atom, nitro group, trifluoromethyl group of 1-pyrrolyl group; R 3  is a bicycloalkyl group, a methyl- or choro-substituted cycloalkyl group, an alkenyl group, a methyl-substituted cycloalkenyl group, 2-methyl-1,3-dithioran-2-yl group or an alkyl group, wherein the alkyl group may be substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group or an alkoxycarbonyl group; R 4  is hydrogen atom or fluorine atom; and X is CR 2  or N. 
     The oxidiazolinone derivative can be used as an insecticide by formulating it into emulsifiable concentrates, wettable powders, dusts, granules, flowable concentrates and poison baits, etc..

The present invention relates to a novel oxadiazolinone derivative, aprocess for producing the same and insecticides containing the same asan active ingredient.

It is described in U.S. Pat. No. 3,385,862 that a certain oxadiazolinonederivative, for example,5-tert-butyl-3-(2,4-dichlorophenyl)-l,3,4-oxadiazolin-2-one, is usefulas an active ingredient of herbicide.

As a result of extensive investigations on compounds having an excellentinsecticidal effect, the present inventors have found that anoxadiazolinone derivative shown by the general formula [I] describedbelow exhibit an extremely high insecticidal effect and haveaccomplished the present invention.

That is, the present invention relates to the oxadiazolinone derivativerepresented by the general formula [I]: ##STR2## wherein R¹ is ahaloalkyl group or a haloalkoxy group; R² is a halogen atom, nitrogroup, trifluoromethyl group or 1-pyrrolyl group; R³ is a bicycloalkylgroup, a methyl- or chloro-substituted cycloalkyl group, an alkenylgroup, a methyl-substituted cycloalkenyl group,2-methyl-l,3-dithioran-2-yl group or an alkyl group, wherein the alkylgroup may be substituted with a halogen atom, an alkoxy group, analkylthio group, an alkylsulfinyl group, an alkylsulfonyl group or analkoxycarbonyl group; R⁴ is hydrogen atom or fluorine atom; and X is CR²or N, (hereafter referred to as the compound(s) of the presentinvention), processes for production thereof, insecticidal compositionscomprising the same as active ingredient, and a method for controllinginsect pests using the same.

In general formula [I], the alkyl group in the haloalkyl group or thealkoxy group in the haloalkoxy group shown by R¹ refers to a grouphaving 1 to 3 carbon atoms, preferably methyl and methoxy. Examples ofthe halogen as the substituent include fluorine atom, chlorine atom orbromine atom, preferably fluorine atom. The most preferred example of R¹is trifluoromethyl. Examples of the halogen atom shown by R² includefluorine atom, chlorine atom or bromine stom, preferably fluorine atomand chlorine atom. As R², a halogen atom and nitro group are preferred.Examples of the alicyclic group shown by R³ are a group of 3- to6-membered ring. The aliphatic group may be exemplified by a grouphaving 1 to 5 carbon atoms except for the substituent, preferably agroup having 2 to 5 carbon atoms. Specific examples of R³ which arepreferred are an alkyl group having 2 to 5 carbon atoms and the halogenatom as a substituent on the alkyl group is exemplified by fluorineatom, chlorine atom and bromine atom. Further the alkoxy group,alkylthio group, alkylsulfinyl group, alkylsulfonyl group oralkoxycarbonyl group also used as the substituent is exemplified bythose having 1 to 3 carbon atoms. Of these substituents, the halogenatom, alkoxy group, alkylthio group, alkylsulfinyl group andalkylsulfonyl group are preferred. More preferred examples are an alkoxygroup having 1 to 2 carbon atoms, an alkylthio group having 1 to 2carbon atoms, an alkylsulfinyl group and alkylsulfonyl group having 1 to2 carbon atoms. Among them, methylthio group is a most preferredsubstituent.

The compounds of the present invention can be produced according to thefollowing reaction scheme (Reaction scheme 1). ##STR3## wherein R¹, R²,R³, R⁴ and X have the same significances as above.

The compounds of the present invention can be produced by reactinghydrazides [II] with phosgene or trichloromethyl chloroformate at about-5° C. to about 150° C. for about 1 to about 24 hours in a solvent inthe presence or absence of an reagent for removing a hydrogen halide.

The compounds of the present invention may also be produced according tothe following reaction scheme (Reaction scheme 2). ##STR4## wherein R¹,R², R³, R⁴ and X have the same significances as above; and Y is ahalogen atom.

The compounds of the present invention can be produced by reactinghalide compounds [III] with oxadiazolinone derivatives [IV] at about 0°C. to about 150° C. for about 1 to about 24 hours in a solvent in thepresence of an reagent for removing a hydrogen halide.

Amounts of the reactants provided for the reactions are described below.In (Reaction scheme 1), 1 to 9 molar equivalents of phosgene ortrichloromethyl chloroformate and 0 to 7 molar equivalents of thereagent for removing a hydrogen halide are used per mole of thehydrazide represented by the general formula [II]. In (Reaction scheme2), 0.5 to 2 molar equivalents of the oxadiazolinone derivativesrepresented by the general formula [IV] and 1 to 4 molar equivalents ofthe reagent for removing a hydrogen halide are used per mole of thehalide compounds represented by the general formula [III].

Examples of the solvent which is used for the both reactions describedabove include aliphatic hydrocarbons such as hexane, heptane, ligroin,petroleum ether, etc.; aromatic hydrocarbons such as benzene, toluene,xylene, etc.; halogenated hydrocarbons such as chloroform, carbontetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, etc.;ethers such as diethyl ether, diisopropyl ether, dioxan,tetrahydrofuran, ethylene glycol dimethyl ether, etc.; ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone,cyclohexanone, etc.; esters such as ethyl acetate, butyl acetate, etc.;nitro compounds such as nitroethane, nitrobenzene, etc.; nitriles suchas acetonitrile, isobutyronitrile, etc.; tertiary amines such aspyridine, triethylamine, N,N-diethylaniline, tributylamine,N-methylmorpholine, etc.; acid amides such as formamide,N,N-dimethylformamide, N,N-dimethylacetamide, etc.; sulfur compoundssuch as dimethylsulfoxide, sulfolane, etc.; or mixtures thereof.

Examples of the reagent of removing hydrogen halide include organicbases such as pyridine, triethylamine, N,N-diethylaniline, etc.;inorganic bases such as sodium hydride, sodium carbonate, potassiumcarbonate, etc.

After completion of the reaction, post-treatment follows in aconventional manner. If necessary and desired, the product may furtherbe purified by chromatography, distillation, recrystallization, etc.

The hydrazide derivatives represented by the general formula [II], theoxadiazolinone derivatives represented by the general formula [IV] andthe halide compounds represented by the general formula [III] which areused as raw materials for the compounds of the present invention areprepared by the methods described in J. March, "Advanced OrganicChemistry", second edition, page 386; Chem. Ber., 82, 121 (1949); andWest German Patent 2,311,638, European Patent 23,100, Belgian Patent865,137 and J. Org. Chem., 25, 1710 (1960), British Patent 1,121,211respectively, or in a manner similar to the methods. Furthermore, thecompounds represented by the general formula [V]: ##STR5## wherein R¹,R², R⁴ and X have the same significances as above; which can be rawmaterials of the hydrazide derivatives represented by the generalformula [II] may be produced by the methods described in, for example,U.S. Pat. No. 4,127,575, U.S. Pat. No. 3,609,158, DE-OS 2,558,399, andJ. Chem. Soc., C. 1971, 167-174.

Examples of the compounds of the present invention are shown in Tables1-1 and 1-2 below.

                  TABLE 1-1                                                       ______________________________________                                         ##STR6##                                                                     R.sup.1                                                                              R.sup.2     R.sup.3          X                                         ______________________________________                                        CF.sub.3                                                                             Cl                                                                     tert-C.sub.4 H.sub.9                CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SCH.sub.3                                                                    CCl                                       CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.3                                                                              CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR7##        CCl                                       CF.sub.3                                                                             Cl                                                                     isoC.sub.3 H.sub.7                                                                   CCl                                                                    CF.sub.3                                                                             Cl          C(CH.sub.3)CH.sub.2                                                                            CCl                                       CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.2 CF.sub.3                                                                     CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OCH.sub.3                                                                    CCl                                       CF.sub.3                                                                             Cl          C(CF.sub.3).sub.2 CH.sub.3                                                                     CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub. 2 COOC.sub.2 H.sub.5                                                          CCl                                       CF.sub.3                                                                             Cl                                                                     sec-C.sub.4 H.sub.9                                                                  CCl                                                                    CF.sub.3                                                                             Cl                                                                                         ##STR8##        CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR9##        CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CCl                                       CF.sub.3                                                                             Cl          C.sub.2 H.sub.5  CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR10##       CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR11##       CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR12##       CCl                                       CF.sub.3                                                                             Cl                                                                     n-C.sub.3 H.sub.7                                                                    CCl                                                                    CF.sub.3                                                                             Cl                                                                                         ##STR13##       CCl                                       CF.sub.3                                                                             NO.sub.2                                                               tert-C.sub.4 H.sub.9                                                                 CNO.sub.2                                                              CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 SCH.sub.3                                                                    CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    CF.sub.2 CF.sub.3                                                                              CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                                                   ##STR14##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                               isoC.sub.3 H.sub.7                                                                   CNO.sub.2                                                              CF.sub.3                                                                             NO.sub.2    C(CH.sub.3)CH.sub.2                                                                            CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    CF.sub.2 CF.sub.2 CF.sub.3                                                                     CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 OCH.sub.3                                                                    CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CF.sub.3).sub.2 CH.sub.3                                                                     CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                               sec-C.sub.4 H.sub.9                                                                  CNO.sub.2                                                              CF.sub.3                                                                             NO.sub.2                                                                                   ##STR15##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                                                   ##STR16##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C.sub.2 H.sub.5  CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                                                   ##STR17##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                                                   ##STR18##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                                                   ##STR19##       CNO.sub.2                                 CF.sub.3                                                                             NO.sub.2                                                               n-C.sub.3 H.sub.7                                                                    CNO.sub.2                                                              CF.sub.3                                                                             NO.sub.2                                                                                   ##STR20##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                     tert-C.sub.4 H.sub.9                                                                 CNO.sub.2                                                              CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SCH.sub.3                                                                    CNO.sub.2                                 CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.3                                                                              CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR21##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                     isoC.sub.3 H.sub.7                                                                   CNO.sub.2                                                              CF.sub.3                                                                             Cl          C(CH.sub.3)CH.sub.2                                                                            CNO.sub.2                                 CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.2 CF.sub.3                                                                     CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OCH.sub.3                                                                    CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CF.sub.3).sub.2 CH.sub.3                                                                     CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                     sec-C.sub.4 H.sub.9                                                                  CNO.sub.2                                                              CF.sub.3                                                                             Cl                                                                                         ##STR22##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR23##       CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CNO.sub.2                                 CF.sub.3                                                                             Cl          C.sub.2 H.sub.5  CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR24##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR25##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR26##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                     n-C.sub.3 H.sub.7                                                                    CNO.sub.2                                                              CF.sub.3                                                                             Cl                                                                                         ##STR27##       CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                     tert-C.sub.4 H.sub.9                                                                 CF                                                                     CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SCH.sub.3                                                                    CF                                        CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.3                                                                              CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR28##       CF                                        CF.sub.3                                                                             Cl                                                                     isoC.sub.3 H.sub.7                                                                   CF                                                                     CF.sub.3                                                                             Cl          C(CH.sub.3)CH.sub.2                                                                            CF                                        CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.2 CF.sub.3                                                                     CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OCH.sub.3                                                                    CF                                        CF.sub.3                                                                             Cl          C(CF.sub.3).sub.2 CH.sub.3                                                                     CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CF                                        CF.sub.3                                                                             Cl                                                                     sec-C.sub.4 H.sub.9                                                                  CF                                                                     CF.sub.3                                                                             Cl                                                                                         ##STR29##       CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR30##       CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CF                                        CF.sub.3                                                                             Cl          C.sub.2 H.sub.5  CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR31##       CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR32##       CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR33##       CF                                        CF.sub.3                                                                             Cl                                                                     n-C.sub.3 H.sub.7                                                                    CF                                                                     CF.sub.3                                                                             Cl                                                                                         ##STR34##       CF                                        CF.sub.3                                                                             Cl                                                                     tert-C.sub.4 H.sub.9                                                                 N                                                                      CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SCH.sub.3                                                                    N                                         CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.3                                                                              N                                         CF.sub.3                                                                             Cl                                                                                         ##STR35##       N                                         CF.sub.3                                                                             Cl                                                                     isoC.sub.3 H.sub.7                                                                   N                                                                      CF.sub.3                                                                             Cl          C(CH.sub.3)CH.sub.2                                                                            N                                         CF.sub.3                                                                             Cl          CF.sub.2 CF.sub.2 CF.sub.3                                                                     N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OCH.sub.3                                                                    N                                         CF.sub.3                                                                             Cl          C(CF.sub.3).sub.2 CH.sub.3                                                                     N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           N                                         CF.sub.3                                                                             Cl                                                                     sec-C.sub.4 H.sub.9                                                                  N                                                                      CF.sub.3                                                                             Cl                                                                                         ##STR36##       N                                         CF.sub.3                                                                             Cl                                                                                         ##STR37##       N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  N                                         CF.sub.3                                                                             Cl          C.sub.2 H.sub.5  N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              N                                         CF.sub.3                                                                             Cl                                                                                         ##STR38##       N                                         CF.sub.3                                                                             Cl                                                                                         ##STR39##       N                                         CF.sub.3                                                                             Cl                                                                                         ##STR40##       N                                         CF.sub.3                                                                             Cl                                                                     n-C.sub.3 H.sub.7                                                                    N                                                                      CF.sub.3                                                                             Cl                                                                                         ##STR41##       N                                         CF.sub.3                                                                             F                                                                      tert-C.sub.4 H.sub.9                                                                 CF                                                                     CF.sub.3                                                                             F           C(CH.sub.3).sub.2 SCH.sub.3                                                                    CF                                        CF.sub.3                                                                             F           CF.sub.2 CF.sub.3                                                                              CF                                        CF.sub.3                                                                             F                                                                                          ##STR42##       CF                                        CF.sub.3                                                                             F                                                                      isoC.sub.3 H.sub.7                                                                   CF                                                                     CF.sub.3                                                                             F           C(CH.sub.3)CH.sub.2                                                                            CF                                        CF.sub.3                                                                             F           CF.sub.2 CF.sub.2 CF.sub.3                                                                     CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 OCH.sub.3                                                                    CF                                        CF.sub.3                                                                             F           C(CF.sub.3).sub.2 CH.sub.3                                                                     CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CF                                        CF.sub. 3                                                                            F                                                                      sec-C.sub.4 H.sub.9                                                                  CF                                                                     CF.sub.3                                                                             F                                                                                          ##STR43##       CF                                        CF.sub.3                                                                             F                                                                                          ##STR44##       CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CF                                        CF.sub.3                                                                             F           C.sub.2 H.sub.5  CF                                        CF.sub.3                                                                             F           C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CF                                        CF.sub.3                                                                             F                                                                                          ##STR45##       CF                                        CF.sub.3                                                                             F                                                                                          ##STR46##       CF                                        CF.sub.3                                                                             F                                                                                          ##STR47##       CF                                        CF.sub.3                                                                             F                                                                      n-C.sub.3 H.sub. 7                                                                   CF                                                                     CF.sub.3                                                                             F                                                                                          ##STR48##       CF                                        CF.sub.3                                                                              ##STR49##                                                             tert-C.sub.4 H.sub.9                                                                 CCl                                                                    CF.sub.3                                                                              ##STR50##  C(CH.sub.3).sub.2 SCH.sub.3                                                                    CCl                                       CF.sub.3                                                                              ##STR51##  CF.sub.2 CF.sub.3                                                                              CCl                                       CF.sub.3                                                                              ##STR52##                                                                                 ##STR53##       CCl                                       CF.sub.3                                                                              ##STR54##                                                             isoC.sub.3 H.sub.7                                                                   CCl                                                                    CF.sub.3                                                                              ##STR55##  C(CH.sub.3)CH.sub.2                                                                            CCl                                       CF.sub.3                                                                              ##STR56##  CF.sub.2 CF.sub.2 CF.sub.3                                                                     CCl                                       CF.sub.3                                                                              ##STR57##  C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CCl                                       CF.sub.3                                                                              ##STR58##  C(CH.sub.3).sub.2 OCH.sub.3                                                                    CCl                                       CF.sub.3                                                                              ##STR59##  C(CF.sub. 3).sub.2 CH.sub.3                                                                    CCl                                       CF.sub.3                                                                              ##STR60##  C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CCl                                       CF.sub.3                                                                              ##STR61##                                                             sec-C.sub.4 H.sub.9                                                                  CCl                                                                    CF.sub.3                                                                              ##STR62##                                                                                 ##STR63##       CCl                                       CF.sub.3                                                                              ##STR64##                                                                                 ##STR65##       CCl                                       CF.sub.3                                                                              ##STR66##  C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CCl                                       CF.sub.3                                                                              ##STR67##  C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CCl                                       CF.sub.3                                                                              ##STR68##  C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CCl                                       CF.sub.3                                                                              ##STR69##  C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CCl                                       CF.sub.3                                                                              ##STR70##  C(CH.sub. 3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                 CCl                                       CF.sub.3                                                                              ##STR71##  C.sub.2 H.sub.5  CCl                                       CF.sub.3                                                                              ##STR72##  C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CCl                                       CF.sub.3                                                                              ##STR73##                                                                                 ##STR74##       CCl                                       CF.sub.3                                                                              ##STR75##                                                                                 ##STR76##       CCl                                       CF.sub.3                                                                              ##STR77##                                                                                 ##STR78##       CCl                                       CF.sub.3                                                                              ##STR79##                                                             n-C.sub.3 H.sub.7                                                                    CCl                                                                    CF.sub.3                                                                              ##STR80##                                                                                 ##STR81##       CCl                                       OCF.sub.3                                                                             ##STR82##                                                             tert-C.sub.4 H.sub.9                                                                 CCl                                                                    OCF.sub.3                                                                             ##STR83##  C(CH.sub.3).sub.2 SCH.sub.3                                                                    CCl                                       OCF.sub.3                                                                            Cl          CF.sub.2 CF.sub.3                                                                              CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR84##       CCl                                       OCF.sub.3                                                                            Cl                                                                     isoC.sub.3 H.sub.7                                                                   CCl                                                                    OCF.sub.3                                                                            Cl          C(CH.sub.3)CH.sub.2                                                                            CCl                                       OCF.sub.3                                                                            Cl          CF.sub.2 CF.sub.2 CF.sub.3                                                                     CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 OCH.sub.3                                                                    CCl                                       OCF.sub.3                                                                            Cl          C(CF.sub.3).sub.2 CH.sub.3                                                                     CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           CCl                                       OCF.sub.3                                                                            Cl                                                                     sec-C.sub.4 H.sub.9                                                                  CCl                                                                    OCF.sub.3                                                                            Cl                                                                                         ##STR85##       CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR86##       CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  CCl                                       OCF.sub.3                                                                            Cl          C.sub.2 H.sub.5  CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR87##       CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR88##       CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR89##       CCl                                       OCF.sub.3                                                                            Cl                                                                     n-C.sub.3 H.sub.7                                                                    CCl                                                                    OCF.sub.3                                                                            Cl                                                                                         ##STR90##       CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 COOCH.sub.3                                                                  N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CF                                        CF.sub.3                                                                              ##STR91##  C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 COOCH.sub.3                                                                  CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CF                                        CF.sub.3                                                                              ##STR92##  C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S-sec-C.sub. 4 H.sub.9                                                       CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        F                                         CF.sub.3                                                                              ##STR93##  C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CF                                        CF.sub.3                                                                              ##STR94##  C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CNO.sub.2                                 CF.sub.3                                                                             Cl           C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                      CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CF                                        CF.sub.3                                                                              ##STR95##  C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       CCl                                       CF.sub.3                                                                             Cl          C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CCl                                       CF.sub.3                                                                             Cl          C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CNO.sub.2                                 CF.sub.3                                                                             Cl          C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CF                                        CF.sub.3                                                                             Cl          C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              N                                         CF.sub.3                                                                             NO.sub.2    C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CNO.sub.2                                 CF.sub.3                                                                             F           C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CF                                        CF.sub.3                                                                              ##STR96##  C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CCl                                       OCF.sub.3                                                                            Cl          C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CF                                        CF.sub.3                                                                              ##STR97##  C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CF                                        CF.sub.3                                                                              ##STR98##  C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          CCl                                       CF.sub.3                                                                             Cl          CH.sub.2 OCH.sub.3                                                                             CCl                                       CF.sub.3                                                                             Cl          CH.sub.2 OCH.sub.3                                                                             CNO.sub.2                                 CF.sub.3                                                                             Cl          CH.sub.2 OCH.sub.3                                                                             CF                                        CF.sub.3                                                                             Cl          CH.sub.2 OCH.sub.3                                                                             N                                         CF.sub.3                                                                             NO.sub.2    CH.sub.2 OCH.sub.3                                                                             CNO.sub.2                                 CF.sub.3                                                                             F           CH.sub.2 OCH.sub.3                                                                             CF                                        CF.sub.3                                                                              ##STR99##  CH.sub.2 OCH.sub.3                                                                             CCl                                       OCF.sub.3                                                                            Cl          CH.sub.2 OCH.sub.3                                                                             CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CF                                        CF.sub.3                                                                              ##STR100## C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CF                                        CF.sub.3                                                                              ##STR101## C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR102##      CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR103##      CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR104##      CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR105##      N                                         CF.sub.3                                                                             NO.sub. 2                                                                                  ##STR106##      CNO.sub.2                                 CF.sub.3                                                                             F                                                                                          ##STR107##      CF                                        CF.sub.3                                                                              ##STR108##                                                                                ##STR109##      CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR110##      CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR111##      CCl                                       CF.sub.3                                                                             Cl                                                                                         ##STR112##      CNO.sub.2                                 CF.sub.3                                                                             Cl                                                                                         ##STR113##      CF                                        CF.sub.3                                                                             Cl                                                                                         ##STR114##      N                                         CF.sub.3                                                                             NO.sub.2                                                                                   ##STR115##      CNO.sub.2                                 CF.sub.3                                                                             F                                                                                          ##STR116##      CF                                        CF.sub.3                                                                              ##STR117##                                                                                ##STR118##      CCl                                       OCF.sub.3                                                                            Cl                                                                                         ##STR119##      CCl                                       CF.sub.3                                                                             CF.sub.3                                                               tert-C.sub.4 H.sub.9                                                                 N                                                                      CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 SCH.sub.3                                                                    N                                         CF.sub.3                                                                             CF.sub. 3   CF.sub.2 CF.sub.3                                                                              N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR120##      N                                         CF.sub.3                                                                             CF.sub.3                                                               isoC.sub.3 H.sub.7                                                                   N                                                                      CF.sub.3                                                                             CF.sub.3    C(CH.sub.3)CH.sub.2                                                                            N                                         CF.sub.3                                                                             CF.sub.3    CF.sub.2 CF.sub.2 CF.sub.3                                                                     N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 OCH.sub.3                                                                    N                                         CF.sub.3                                                                             CF.sub.3    C(CF.sub.3).sub.2 CH.sub.3                                                                     N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                           N                                         CF.sub.3                                                                             CF.sub.3                                                               sec-C.sub.4 H.sub.9                                                                  N                                                                      CF.sub.3                                                                             CF.sub.3                                                                                   ##STR121##      N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR122##      N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                            N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                             N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                          N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                     N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                  N                                         CF.sub.3                                                                             CF.sub.3    C.sub.2 H.sub.5  N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR123##      N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR124##      N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR125##      N                                         CF.sub.3                                                                             CF.sub.3                                                               n-C.sub.3 H.sub.7                                                                    N                                                                      CF.sub.3                                                                             CF.sub.3                                                                                   ##STR126##      N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 COOCH.sub.3                                                                  N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                         N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                        N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                         N                                         CF.sub. 3                                                                            CF.sub.3    C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                       N                                         CF.sub.3                                                                             CF.sub.3    C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                              N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                             N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                          N                                         CF.sub.3                                                                             CF.sub.3    CH.sub.2 OCH.sub.3                                                                             N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                         N                                         CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                        N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR127##      N                                         CF.sub.3                                                                             CF.sub.3                                                                                   ##STR128##      N                                         CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CCl                                       CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CNO.sub.2                                 CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CF                                        CF.sub.3                                                                             Cl          C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 N                                         CF.sub.3                                                                             NO.sub.2    C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CNO.sub.2                                 CF.sub.3                                                                             F           C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CF                                        CF.sub.3                                                                              ##STR129## C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CCl                                       OCF.sub.3                                                                            Cl          C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 CCl                                       CF.sub.3                                                                             CF.sub.3    C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                 N                                         ______________________________________                                    

                  TABLE 1-2                                                       ______________________________________                                         ##STR130##                                                                   R.sup.1 R.sup.2   R.sup.3         X                                           ______________________________________                                        CF.sub.3                                                                              Cl                                                                    tert-C.sub.4 H.sub.9              CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SCH.sub.3                                                                   CCl                                         CF.sub.3                                                                              Cl        CF.sub.2 CF.sub.3                                                                             CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR131##     CCl                                         CF.sub.3                                                                              Cl                                                                    isoC.sub.3 H.sub.7                                                                    CCl                                                                   CF.sub.3                                                                              Cl        C(CH.sub.3)CH.sub.2                                                                           CCl                                         CF.sub.3                                                                              Cl        CF.sub.2 CF.sub.2 CF.sub.3                                                                    CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                 CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 OCH.sub.3                                                                   CCl                                         CF.sub.3                                                                              Cl        C(CF.sub.3).sub.2 CH.sub.3                                                                    CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                          CCl                                         CF.sub.3                                                                              Cl                                                                    sec-C.sub.4 H.sub.9                                                                   CCl                                                                   CF.sub.3                                                                              Cl                                                                                       ##STR132##     CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR133##     CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                           CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                            CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                         CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                    CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                 CCl                                         CF.sub.3                                                                              Cl        C.sub.2 H.sub.5 CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                             CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR134##     CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR135##     CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR136##     CCl                                         CF.sub.3                                                                              Cl                                                                    n-C.sub.3 H.sub.7                                                                     CCl                                                                   CF.sub.3                                                                              Cl                                                                                       ##STR137##     CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 COOCH.sub.3                                                                 CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                        CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                       CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                        CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                      CCl                                         CF.sub.3                                                                              Cl        C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                             CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                            CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                         CCl                                         CF.sub.3                                                                              Cl        CH.sub.2 OCH.sub.3                                                                            CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                        CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                       CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR138##     CCl                                         CF.sub.3                                                                              Cl                                                                                       ##STR139##     CCl                                         CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                CCl                                         CF.sub.3                                                                              F                                                                     tert-C.sub. 4 H.sub.9                                                                 CCl                                                                   CF.sub.3                                                                              F         C(CH.sub.3).sub.2 SCH.sub.3                                                                   CCl                                         CF.sub.3                                                                              F         CF.sub.2 CF.sub.3                                                                             CCl                                         CF.sub.3                                                                              F                                                                                        ##STR140##     CCl                                         CF.sub.3                                                                              F                                                                     isoC.sub.3 H.sub.7                                                                    CCl                                                                   CF.sub.3                                                                              F         C(CH.sub.3)CH.sub.2                                                                           CCl                                         CF.sub.3                                                                              F         CF.sub.2 CF.sub.2 CF.sub.3                                                                    CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                 CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 OCH.sub.3                                                                   CCl                                         CF.sub.3                                                                              F         C(CF.sub.3).sub.2 CH.sub.3                                                                    CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                          CCl                                         CF.sub.3                                                                              F                                                                     sec-C.sub.4 H.sub.9                                                                   CCl                                                                   CF.sub.3                                                                              F                                                                                        ##STR141##     CCl                                         CF.sub.3                                                                              F                                                                                        ##STR142##     CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                           CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                            CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S-n-C.sub. 3 H.sub.7                                                        CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                    CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                 CCl                                         CF.sub.3                                                                              F         C.sub.2 H.sub.5 CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                             CCl                                         CF.sub.3                                                                              F                                                                                        ##STR143##     CCl                                         CF.sub.3                                                                              F                                                                                        ##STR144##     CCl                                         CF.sub.3                                                                              F                                                                                        ##STR145##     CCl                                         CF.sub.3                                                                              F                                                                     n-C.sub.3 H.sub.7                                                                     CCl                                                                   CF.sub.3                                                                              F                                                                                        ##STR146##     CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 COOCH.sub.3                                                                 CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                        CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                       CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                        CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                      CCl                                         CF.sub.3                                                                              F         C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                             CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                            CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                         CCl                                         CF.sub.3                                                                              F         CH.sub.2 OCH.sub.3                                                                            CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                        CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                       CCl                                         CF.sub.3                                                                              F                                                                                        ##STR147##     CCl                                         CF.sub.3                                                                              F                                                                                        ##STR148##     CCl                                         CF.sub.3                                                                              F         C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                CCl                                         CF.sub.3                                                                              Cl                                                                    tert-C.sub.4 H.sub.9                                                                  CF                                                                    CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SCH.sub.3                                                                   CF                                          CF.sub.3                                                                              Cl        CF.sub.2 CF.sub.3                                                                             CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR149##     CF                                          CF.sub.3                                                                              Cl                                                                    isoC.sub.3 H.sub.7                                                                    CF                                                                    CF.sub.3                                                                              Cl        C(CH.sub.3)CH.sub.2                                                                           CF                                          CF.sub.3                                                                              Cl        CF.sub.2 CF.sub.2 CF.sub.3                                                                    CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                 CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 OCH.sub.3                                                                   CF                                          CF.sub.3                                                                              Cl        C(CF.sub.3).sub.2 CH.sub.3                                                                    CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                                                          CF                                          CF.sub.3                                                                              Cl                                                                    sec-C.sub.4 H.sub.9                                                                   CF                                                                    CF.sub.3                                                                              Cl                                                                                       ##STR150##     CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR151##     CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                           CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                            CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                         CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 C.sub.2 H.sub.5                                                    CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 SO.sub.2 -n-C.sub.3 H.sub.7                                                 CF                                          CF.sub.3                                                                              Cl        C.sub.2 H.sub.5 CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                             CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR152##     CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR153##     CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR154##     CF                                          CF.sub.3                                                                              Cl                                                                    n-C.sub.3 H.sub.7                                                                     CF                                                                    CF.sub.3                                                                              Cl                                                                                       ##STR155##     CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 COOCH.sub.3                                                                 CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-isoC.sub.3 H.sub.7                                                        CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-sec-C.sub.4 H.sub.9                                                       CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-isoC.sub.4 H.sub.9                                                        CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S-tert-C.sub.4 H.sub.9                                                      CF                                          CF.sub.3                                                                              Cl        C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                             CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                            CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-n-C.sub.3 H.sub.7                                                         CF                                          CF.sub.3                                                                              Cl        CH.sub.2 OCH.sub.3                                                                            CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-isoC.sub.4 H.sub.9                                                        CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 O-sec-C.sub.4 H.sub.9                                                       CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR156##     CF                                          CF.sub.3                                                                              Cl                                                                                       ##STR157##     CF                                          CF.sub.3                                                                              Cl        C(CH.sub.3).sub.2 S(O)CH.sub.3                                                                CF                                          ______________________________________                                    

Examples of harmful insects against which the compounds of the presentinvention exhibit remarkable effects include the following:

Harmful Insects Belonging to Hemiptera

Planthoppers such as small brown planthopper (Laodelphax striatellus),brown planthopper (Nilaparvata lugens), white-backed rice planthopper(Sogatella furcifera), etc.; leafhoppers such as green rice leafhopper(Nephotettix cinticeps), (Nephotettix virescens), etc.; aphids, bugs,whiteflies, scales, lace bugs, psyllids, etc.

Lepidoptera

Pyralid moths such as rice stem borer (Chilo suppressalis), riceleafroller (Cnaphalocrocis medinalis), Indian meal moth (Plodiainterpunctella), etc.; moths such as tobacco cutworm (Spodopteralitura), rice armyworm (Pseudaletia separata), cabbage armyworm(Mamestra brassicae), etc.; Pieridae such as common cabbageworm (Pierisrapae crucivora), etc.; Tortricidae or tortricid moths such asAdoxophyes spp., Grapholita spp., etc.; Carposinidae, lyonetiid moths(Lyonetiidae), tussock moths (Lymantriidae), beet semi-looper(Autographa nigrisigna); harmful insects belonging to Agrothis spp. suchas turnip cutworm (Agrothis segetum), black cutworm (Agrothis ipsilon);harmful insects belonging to Hiliothis spp.; diamondback moth (Plutellaxylostella), clothes moths (Tineidae), casemaking clothes moth (Tineatranslucens), webbing clothes moth (Tineola bisselliella); etc.

Harmful Insects Belonging to Diptera

Mosquitos such as common mosquito (Culex pipiens pallens), Culextritaeniorhynchus, etc.; Aedes spp. such as Aedes aegypti, Aedesalbopictus, etc.; midges (Chironomidae); Muscidae such as housefly(Musca domestica), false stablefly (Muscina stabulans), etc.Calliphoridae; Sarcophagidae; lesser housefly (Fannia canicularis);Anthomyiidae or anthomyiid flies such as seedcorn maggot (Deliaplatura), onion maggot (Delia antiqua), etc.; fruit flies (Tephritidae);small fruit flies (Drosophilidae); moth flies (Psychodidae); black flies(Simuliidae); Tabanidae; stable flies (Stomoxyidae); etc. Harmfulinsects belonging to Coleoptera:

Corn root worms such as western corn rootworm (Diabrotica virgifera),southern corn root worm (Diabrotica undecimpunctata), etc.; scarabs(Scarabaeidae) such as cupreous chafer (Anomala cuprea), soybeen beetle(Anomala rufocuprea), etc.; weevils such as maize weevil (Sitophiluszeamais), rice water weevil (Lissorhoptrus oryzophilus), adzuki beenweevil (Callosobruchys chineneis), etc.; darkling beetles(Tenebrionidae) such as yellow mealworm (Tenebrio molitor), red fluorbeetle (Tribolium castaneum), etc.; leaf beetles (Chrysomelidae) such ascucrubit leaf beetle (Aulacophora femoralis), striped flea beetles(Phyllotreta striolata), etc.; Anobiidae; Epilachna spp. such astwenty-eight-spotted ladybirds (Epilachna vigintioctopunctata), etc.;powderpost beetles (Lyctidae); false powderpost beetles (Bostrychidae),Cerambycidae; robe beetle (Paederus fusipes), etc.

Harmful Insects Belonging to Dictyoptera

German cockroach (Blattella germanica), smokybrown cockroach(Periplaneta fuliginosa), American cockroach (Periplaneta americana),brown cockroach (Periplaneta brunnea), oriental cockroach (Blattaorientalis), Japanese cockroach (Periplaneta japonica), etc.

Harmful Insects Belonging to Thysanoptera

Thrips palmi, flower thrips (Thrips hawaiiensis), etc.

Harmful Insects Belonging to Hymenoptera

ants (Formicidae); hornets (Vespidae); bethylid wasps (Bethylidae);sawflies (Tenthredinidae) such as cabbage sawfly (Athalia rosaeruficornis), etc.

Harmful Insects Belonging to Orthoptera

mole crickets (Gryllotalpidae); grasshoppers (Acrididae), etc.;

Harmful Insects Belonging to Aphaniptera

Purex irritans, etc.

Harmful Insects Belonging to Anoplura

Pediculus humanus capitis, Pythirus pubis, etc.

Harmful Insects Belonging to Isoptera

Reticulitermes speratus, Formosan subterranean termite (Coptotermesformosanus), etc.

Moreover, the compounds of the present invention are very effective tothe insects which develop the resistance against conventionalinsecticides.

In the case that the compounds of the present invention are used as theactive ingredient of insecticidal compositions, the compounds may beused as they are, without adding any other components but in general,the compounds are mixed with a solid carrier, a liquid carrier, agaseous carrier, a feed, etc. and, if necessary and desired, the mixtureis further supplemented with a surfactant and other adjuvants used toprepare insecticidal preparations and prepared into forms such as oilsprays, emulsifiable concentrates, wettable powders, flowableconcentrates, granules, dusts, aerosol, fumigants (fogging, etc.),poison bait, etc.

These formulations contain generally 0.01 to 95% by weight of thecompounds of the present invention as the active ingredient.

Examples of the solid carrier used for making formulations include finepowders or granulates, etc. of clays (kaolin clay, diatomaceous earth,synthetic hydrated silicon dioxide, bentonite, Fubasami clay terra alba,etc.), talc, ceramics, other inorganic minerals (sericite, quartz,sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),chemical fertilizers (ammonium sulfate, ammonium phosphate, ammoniumnitrate, urea, ammonium chloride, etc.), etc. Examples of the liquidcarrier include water, alcohols (methanol, ethanol, etc.), ketones(acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene,toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatichydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters(ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile,isobutyronitrile, etc.), ethers (diisopropyl ether, dioxan, etc.), acidamides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenatedhydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride,etc.), dimethylsulfoxide; vegetable oils such as soybean oil, cottonseed oil, etc. Examples of the gaseous carrier, i.e., propellant,include freon gas, butane gas, LPG (liquefied petroleum gas), dimethylether, carbon dioxide, etc.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates,alkylaryl sulfonates, alkyl aryl ethers and polyoxyethylene derivativesthereof, polyethylene glycol ether, polyvalent alcohol esters, sugaralcohol derivatives, etc.

Examples of the adjuvants such as binders, dispersing agents, etc. forformulations include casein, gelatin, polysaccharides (starch powders,gum arabic, cellulose derivatives, alginic acid, etc.), ligninderivatives, bentonite, sugars, synthetic water-soluble high molecularsubstances (polyvinyl alcohol, polyvinyl-pyrrolidone, polyacrylic acid,etc.). Examples of the stabilizer include PAP (acidic isopropylphosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils, mineral oils, surfactants, fatty acids or estersthereof, and the like.

As a base material for the poison baits, there are, for example, feedcomponents such as crop powders, essential vegetable oil, sugars,crystalline cellulose etc.; antioxidants such as dibutylhydroxytoluene,nordihydroguaiaretic acid, etc.; preservatives such as dehydroaceticacid, etc.; feeding error preventing agents such as red peper powders,etc.; incentive flavor such as cheese flavor, onion flavor, etc.

The thus obtained formulations may be used as they are or after dilutingwith water, etc. Alternatively, the formulations may be used asadmixture with other insecticides, nematocides, acaricides,bacteriocides, herbicides, plant growth regulators, synergistic agents,fertilizers, soil conditioners, animal feed, etc., or may also be usedsimultaneously with them, without mixing therewith.

Where the compounds of the present invention are used as insecticidesfor agricultural use, the dose is generally 0.1 g to 100 g per 10 ares;when emulsifiable concentrates, wettable powders, flowable concentrates,etc. are used after diluting them with water, the concentration is 1 ppmto 500 ppm. Granules, dusts, etc. may be used as they are, withoutdiluting them. For purposes of household and public hygiene,emulsifiable concentrates, wettable powders, flowable concentrates, etc.are diluted with water in a concentration of 1 ppm to 500 ppm; oils,aerosol, fumigants, poison baits, etc. may be used as they are.

These doses and concentrations may vary depending upon kind offormulations, timing for application, place applied, method forapplication, kinds of insect, condition of damages, etc. and may beincreased or decreased, irrespective of the ranges set forth above.

Hereafter the present invention is described in more detail, byreferring to production examples, formulation examples and test examplesbut is not deemed to these examples.

PRODUCTION EXAMPLE 1 (Production of Compound No. (1))

In 4.6 ml (8.9 mmols) of 20% phosgene-toluene solution, 0.33 g (1 mmol)ofN'-(2,6-dichloro-4-trifluoromethylphenyl)-2,2-dimethylpropionhydrazidewas heated to reflux for 16 hours (inner temperature of 80° C.). Then,an excess of phosgene and toluene was distilled off. After the residuewas dissolved in 5 ml of methylene chloride, 0.65 g (6.4 mmols) oftriethylamine was added to the solution and the mixture was heated toreflux for 30 minutes. Next, the mixture was washed with water, driedover anhydrous sodium sulfate and then concentrated under reducedpressure. The thus obtained crude product was subjected to silica gelcolumn chromatography to give 0.16 g of5-(1,1-dimethylethyl)-3-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.

m.p. 143.0° C.

PRODUCTION EXAMPLE 2 (Production of Compound No. (2))

To a mixture of 0.35 g (1 mmol) ofN'-(2,6-dichloro-4-trifluoromethylphenyl)-2-methyl-2-methylthiopropionhydrazide,0.25 g (2.5 mmols) of triethylamine and 5 ml of dioxan was dropwiseadded 0.24 g (1.2 mmol) of trichloromethyl chloroformate. Aftercompletion of the dropwise addition, the mixture was heated to refluxfor 3 hours. The mixture was concentrated under reduced pressure and theresidue was taken up in ether. After washing with water and saturatedsodium bicarbonate aqueous solution, the solution was dried overanhydrous sodium sulfate and then concentrated under reduced pressure.The thus obtained crude product was subjected to silica gel columnchromatography to give 0.17 g of5-(1-methyl-l-methylthioethyl)-3-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.

m.p. 92.0° C.

PRODUCTION EXAMPLE 3 (Production of Compound No. (3))

After 44 mg (1.1 mmol) of 60% sodium hydride was added to a solution of0.14 g (1 mmol) of 5-(1-methylcyclopropyl)-1,3,4-oxadiazolin-2-one in 5ml of N,N-dimethylformamide at room temperature, the mixture was stirredat the same temperature for 15 minutes. To the mixture was added 0.25 g(1 mmol) of 3,4,5-trichlorobenzotrifluoride followed by heating a 80° C.for 6 hours. After cooling, the mixture was poured into water andextracted with ethyl acetate. After drying over magnesium sulfate, theextract was concentrated under reduced pressure to give the crudeproduct. The crude product was subjected to silica gel columnchromatography to give 35 mg of5-(1-methylcyclopropyl)-3-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazoline-2-one.

m.p. 107.1° C.

PRODUCTION EXAMPLE 4 (Production of Compound No. (4))

A mixture of 0.35 g (1 mmol) ofN'-(2,6-dinitro-4-trifluoromethylphenyl)-2,2-dimethylpropionhydrazide,0.3 g (3.1 mmols) of phosgene and 2.1 ml of toluene was heated to refluxfor 2.5 hours (inner temperature of 59° C.). A solution (0.7 ml) of 0.1g (1 mmol) of phosgene in toluene was further added to the reactionmixture followed by heating to reflux for further 2.5 hours. An excessof phosgene and toluene were distilled off and the residue was taken upin 20 ml of ether. After washing with saturated sodium chloride aqueoussolution, the solution was dried over anhydrous sodium sulfate and thenconcentrated under reduced pressure. The thus obtained crude product wassubjected to silica gel column chromatography to give 0.17 g of5-(1,1-dimethylethyl)-3-(2,6-dinitro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.

m.p. 146.0° C.

Compounds produced according to Production Examples are shown in Table2.

                                      TABLE 2                                     __________________________________________________________________________     ##STR158##                                                                   Compound No.                                                                          R.sup.1                                                                          R.sup.2                                                                          R.sup.3     X   Physical constant                               __________________________________________________________________________     (1)    CF.sub.3                                                                         Cl                                                                 tert-C.sub.4 H.sub.9      CCl m.p. 143.0° C.                            (2)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SCH.sub.3                                                               CCl m.p. 92.0° C.                             (3)    CF.sub.3                                                                         Cl                                                                                ##STR159## CCl m.p. 107.1° C.                            (4)    CF.sub.3                                                                         NO.sub.2                                                           tert-C.sub.4 H.sub.9                                                                  CNO.sub.2                                                                        m.p. 146.0° C.                                               (5)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SO.sub.2 CH.sub.3                                                       CCl m.p. 153.2° C.                            (6)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SC.sub.2 H.sub.5                                                        CCl n.sub.D.sup.24.0  1.5152                         (7)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 S-n-C.sub.3 H.sub.7                                                     CCl n.sub.D.sup.24.0 1.5159                          (8)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                         CCl m.p. 67.2° C.                             (9)    CF.sub.3                                                                         Cl CF.sub.2 CF.sub.3                                                                         CCl n.sub.D.sup.24.0 1.4421                         (10)    CF.sub.3                                                                         NO.sub.2                                                                         C(CH.sub.3).sub.2 SCH.sub.3                                                               CNO.sub.2                                                                         m.p. 121.7° C.                           (11)    CF.sub.3                                                                         NO.sub.2                                                                          ##STR160## CNO.sub.2                                                                         m.p. 144.2° C.                           (12)    CF.sub.3                                                                         Cl                                                                 tert-C.sub.4 H.sub.9                                                                  CF m.p. 94.4° C.                                               (13)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SCH.sub.3                                                               CF  n.sub.D.sup.22.5 1.4919                         (14)    CF.sub.3                                                                         Cl                                                                                ##STR161## CF  m.p. 81.7° C.                            (15)    CF.sub.3                                                                         Cl                                                                                ##STR162## CF  n.sub.D.sup.25.2 1.4879                         (16)    CF.sub.3                                                                         Cl                                                                 tert-C.sub.4 H.sub.9                                                                  N  n.sub.D.sup.25.2 1.4842                                            (17)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SCH.sub.3                                                               N   n.sub.D.sup.25.2 1.5152                         (18)    CF.sub.3                                                                         Cl                                                                                ##STR163## CCl m.p. 118.1° C.                           (19)    CF.sub.3                                                                         Cl                                                                 tert-C.sub.4 H.sub.9                                                                  CNO.sub.2                                                                        m.p. 109.7° C.                                              (20)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 OC.sub.2 H.sub.5                                                        CCl m.p. 62.7° C.                            (21)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 OCH.sub.3                                                               CCl n.sub.D.sup.24.2 1.4949                         (22)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SCH.sub.3                                                               CNO.sub.2                                                                         m.p. 100.5° C.                           (23)    C.sub.3 F.sub.7                                                                  Cl C(CH.sub.3).sub.2 SCH.sub.3                                                               CCl n.sub.D.sup.22.6 1.4853                         (24)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 SOCH.sub.3                                                              CCl n.sub.D.sup.25.2 1.5141                         (25)    CF.sub.3                                                                         F  C(CH.sub.3).sub.2 SCH.sub.3                                                               CF  n.sub.D.sup.24.2 1.4874                         (26)    CF.sub.3                                                                         Cl C(CH.sub.3).sub.2 O-isoC.sub.3 H.sub.7                                                    CCl n.sub.D.sup.24.3 1.4869                         (27)    CF.sub.3                                                                         Cl C(CH.sub.2)CH.sub.3                                                                       CCl m.p. 93.2° C.                            (28)    CF.sub.3                                                                         Cl CF.sub.2 CF.sub.3                                                                         CF  n.sub.D.sup.23.8 1.4269                         (29)    CF.sub.3                                                                         CF.sub.3                                                                         C(CH.sub.3).sub. 2 SCH.sub.3                                                              N   n.sub.D.sup.22.7 1.4781                         (30)    CF.sub.3                                                                         Cl                                                                                ##STR164## CCl n.sub.D.sup.26.0 1.5092                         __________________________________________________________________________

Next, Formulation examples are shown, wherein parts are all by weightand the compounds of the present invention are designated by thecompound numbers shown in Table 2.

FORMULATION EXAMPLE 1 Emulsifiable Concentrate

After 10 parts each of Compounds (1) through (30) of the presentinvention are dissolved in 35 parts of xylene and 35 parts ofdimethylformamide, 14 parts of polyoxyethylene styrylphenyl ether and 6parts of calcium dodecylbenzenesulfonate are added to the solutions. Theresulting mixtures are thoroughly mixed stirred to give 10% emulsifiableconcentrate, respectively.

FORMULATION EXAMPLE 2 Wettable Powder

After 20 parts of Compound (2) of the present invention are added to amixture of 4 parts of sodium laurylsulfate, 2 parts of calciumligninsulfonate, 20 parts of synthetic hydrated silicon dioxide finepowders and 54 parts of diatomaceous earth, the mixture is mixed andstirred with a juice mixer to give 20% wettable powder.

FORMULATION EXAMPLE 3 Granule (In the Case of Solid Active Ingredient)

After 5 parts of synthetic hydrated silicon dioxide fine powders, 5parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55parts of clay are added to 5 parts of Compound (5) of the presentinvention, the mixture is thoroughly mixed and stirred. A suitableamount of water is further added to the mixture followed by stirring.The mixture is granulated with a granulator and air-dried to give 5%granule.

FORMULATION EXAMPLE 4 Dust

After 1 part of Compound (13) of the present invention is dissolved in aappropriate amount of acetone, 5 parts of synthetic hydrated silicondioxide fine powders, 0.3 part of PAP and 93.7 parts of clay are addedto the solution. The mixture is mixed and stirred with a juice mixer andacetone is evaporated off to give 1% dust.

FORMULATION EXAMPLE 5 Flowable Concentrate (In the Case of Solid ActiveIngredient)

After 20 parts of Compound (3) of the present invention and 1.5 part ofsorbitan trioleate are mixed with 28.5 parts of an aqueous solutioncontaining 2 parts of polyvinyl alcohol, the mixture is finely divided(less than 3μ in particle diameter) with a sand grinder. Then, 40 partsof aqueous solution containing 0.05 part of xanthane gum and 0.1 part ofaluminum magnesium silicate are added to the powders and 10 parts ofpropylene glycol are further added thereto. The mixture is thoroughlymixed and stirred to give 20% flowable concentrate for aqueoussuspension.

FORMULATION EXAMPLE 6 Oil Spray

After 0.1 part of Compound (2) of the present invention is dissolved in5 parts of xylene and 5 parts of trichloroethane, the solution is mixedwith 89.9 parts of deodorized kerosene to give 0.1% oil spray.

FORMULATION EXAMPLE 7 Oil-Based Aerosol

After 0.1 part of Compound (2) of the present invention, 0.2 part oftetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and59.6 parts of deodorized kerosene are mixed with each other anddissolved. The solution is filled in an aerosol container. After a valveis mounted to the container, 30 parts of propellant (liquefied petroleumgas) are filled under pressure through the valve to give oil-basedaerosol.

FORMULATION EXAMPLE 8 Water-Based Aerosol

After 0.2 part of Compound (2) of the present invention, 0.2 part ofd-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts ofdeodorized kerosene and 1 part of emulsifier [ATMOS 300 (registeredtrademark, Atlas Chemical Co., Ltd.)] are mixed with each other anddissolved. The solution and 50 parts of distilled water are filled in anaerosol container. After a valve is mounted to the container, 40 partsof propellant (liquefied petroleum gas) are filled under pressurethrough the valve to give water-based aerosol.

FORMULATION EXAMPLE 9 Mosquito Coil

After 0.3 g of d-allethrin is added to 0.3 g of Compound (2) of thepresent invention, the mixture is dissolved in 20 ml of acetone. Thesolution is then uniformly mixed with 99.4 g of carrier formosquito-coil (taba powder : sake lees powder wood powder of 4:3:3) withstirring and 120 ml of water is then added to the mixture. The mixtureis thoroughly kneaded, molded and dried to give mosquito-coil.

FORMULATION EXAMPLE 10 Electric Mosquito Mat

Acetone is added to 0.4 g of Compound (2) of the present invention, 0.4g of d-allethrin and 0.4 g of piperonyl butoxide to dissolve and makethe whole volume 10 ml. This solution, 0.5 ml, is uniformly impregnatedwith a base material for electric mat (a mixture of cotton linter andpulp solidified in a plate-like form) having 2.5 cm×1.5 cm and athickness of 0.3 cm to give an electric mosquito mat.

FORMULATION EXAMPLE 11 Fumigant

After 100 mg of Compound (13) of the present invention is dissolved in aappropriate amount of acetone, the solution is impregnated with a porousceramic plate having 4.0 cm×4.0 cm and a thickness of 1.2 cm to give afumigant.

FORMULATION EXAMPLE 12 Poison Bait

After 10 mg of Compound (13) of the present invention is dissolved in a0.5 ml acetone, the solution is applied to 5 g of the powder of dryanimal food. The powder is dried to give a 0.5% poison bait.

Next, effectiveness of the compounds of the present invention as theactive ingredient of insecticidal compositions is described below, withreference to test examples, wherein the compounds of the presentinvention are designated by the compound numbers shown in Table 2 andcompounds used for comparison and control are designated by the compoundnumbers shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Compound                                                                      Symbol  Chemical Structure    Note                                            ______________________________________                                        (A)                                                                                    ##STR165##           Compound described in U.S. Pat. No.                                           3,385,862                                       ______________________________________                                    

TEST EXAMPLE 1 (Insecticidal Test on Nymphs of Brown Planthopper)

The emulsifiable concentrate of the test compound prepared according toFormulation Example 1 was diluted with water (corresponding to 500 ppm)and a rice plant seedling (length of about 12 cm) was immersed in thedilution for a munute. After air-drying, the rice plant seedling was putin a test tube and about 30 nymphs of brown planthopper (Nilaparvatalugens) were released. Six days after, the nymphs were observed if theywere alive or dead. Criterion for the judgement is as follows.

a: no insect was alive.

b: alive insects were 5 or less.

c: alive insects were 6 or more.

The results are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Test Compound   Efficacy                                                      ______________________________________                                         (1)            a                                                              (2)            a                                                              (3)            a                                                              (5)            a                                                             (10)            a                                                             (12)            a                                                             (13)            a                                                             (14)            a                                                             (15)            a                                                             (16)            a                                                             (17)            a                                                             (18)            a                                                             (19)            a                                                             (20)            a                                                             (21)            a                                                             (22)            a                                                             (23)            a                                                             (24)            a                                                             (25)            a                                                             (26)            a                                                             (27)            a                                                             (29)            a                                                             (30)            a                                                             (A)             c                                                             Untreated       c                                                             ______________________________________                                    

TEST EXAMPLE 2 (Insecticidal Test on Southern Corn Rootworm)

On the bottom of a polyethylene cup having a diameter of 5.5 cm, afilter paper which is of the same size was laid down and 1 ml of anaqueous dilution (500 or 50 ppm) of the emulsifiable concentrate of thetest compound prepared according to Formulation Example 1 was droppedonto the filter paper and one corn sprout was put as feed. About 30 eggsof southern corn rootworm (Diabrotica undecimpunctata) were put in thecup. Eight days after the cup was covered, dead or alive larvae hatchedwere examined. Criterion for the judgement is as follows.

a: no insect was alive.

b: alive insects were 5 or less.

c: alive insects were 6 or more.

The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                       Efficacy                                                       Test Compound    500 ppm  50 ppm                                              ______________________________________                                         (1)             a        a                                                    (2)             a        a                                                    (3)             a        a                                                    (5)             a        a                                                   (12)             a        a                                                   (13)             a        a                                                   (14)             a        a                                                   (16)             a        a                                                   (18)             a        a                                                   (19)             a        a                                                   (21)             a        a                                                   (22)             a        a                                                   (24)             a        a                                                   (25)             a        a                                                   (26)             a        a                                                   (27)             a        a                                                   (29)             a        a                                                   Untreated        c        c                                                   ______________________________________                                    

TEST EXAMPLE 3 (Insecticidal Test on Common Mosquito)

The emulsifiable concentrate of the test compound prepared according toFormulation Example 1 was diluted with water and 0.7 ml of the dilutionwas added to 100 ml of ion exchange water (concentration of theeffective ingredient was 3.5 ppm). In the mixture were released 20 lastinstar larvae of common mosquito (Culex pipiens pallens). One day afterthe release, mortality was examined.

Criterion for the judgement is as follows.

a: 90% or more

b: not less than 10% but less than 90%

c: less than 10%

The results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Test Compound  Mortality (%)                                                  ______________________________________                                         (1)           a                                                               (2)           a                                                               (3)           a                                                               (5)           a                                                              (12)           a                                                              (13)           a                                                              (14)           a                                                              (20)           a                                                              (21)           a                                                              (22)           a                                                              (23)           a                                                              (24)           a                                                              (25)           a                                                              (29)           a                                                              (30)           a                                                              (A)            c                                                              Untreated      c                                                              ______________________________________                                    

TEST EXAMPLE 4 (Insecticidal Test on German Cockroach)

On the bottom of a polyethylene cup having a diameter of 5.5 cm, afilter paper which is of the same size was laid down and 0.7 ml of anaqueous dilution (500 ppm) of the emulsifiable concentrate of the testcompound prepared according to Formulation Example 1 was dropped ontothe filter paper. As feed, 30 mg of sucrose was uniformly spreadthereon. In the cup, 10 adult males of German cockroach (Blattellagermanica) were released. Six days after the cup was covered, dead oralive insects were examined to determine mortality.

The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Test Compound  Mortality (%)                                                  ______________________________________                                         (1)           100                                                             (2)           100                                                             (5)           100                                                            (10)           100                                                            (12)           100                                                            (13)           100                                                            (14)           100                                                            (16)           100                                                            (17)           100                                                            (19)           100                                                            (21)           100                                                            (22)           100                                                            (23)           100                                                            (24)           100                                                            (25)           100                                                            (26)           100                                                            (29)           100                                                            (A)             0                                                             Untreated       0                                                             ______________________________________                                    

TEST EXAMPLE 5 (Insecticidal Test on Housefly)

On the bottom of a polyethylene cup having a diameter of 5.5 cm, afilter paper which is of the same size was laid down and 0.7 ml of anaqueous dilution (500 ppm) of the emulsifiable concentrate of the testcompound prepared according to Formulation Example 1 was dropped ontothe filter paper. As feed, 30 mg of sucrose was uniformly spreadthereon. In the cup, 10 adult females of housefly (Musca domestica) werereleased. Fourty eight hours after the cup was covered, dead or aliveinsects were examined to determine mortality (2 replications). Theresults are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Test Compound  Mortality (%)                                                  ______________________________________                                         (2)           100                                                            (13)           100                                                            (24)           100                                                            (A)            100                                                            Untreated       0                                                             ______________________________________                                    

What is claimed is:
 1. An oxadiazolinone derivative represented by thegeneral formula: ##STR166## wherein R¹ is a C₁ -C₃ haloalkyl group or aC₁ -C₃ haloalkoxy group; R² is a halogen atom, nitro group,trifluoromethyl group or 1-pyrrolyl group; R³ is a C₇ bicycloalkylgroup, a methyl- or chloro-substituted C₃ -C₆ cycloalkyl group, a C₂ -C₅alkenyl group, a methyl-substituted C₅ -C₆ cycloalkenyl group,2-methyl-1,3-dithioran-2-yl group or a C₁ -C₅ alkyl group, wherein thealkyl group may be substituted with a halogen atom, a C₁ -C₃ alkoxygroup, a C₁ -C₃ alkylthio group, a C₁ -C₃ alkylsulfinyl group, a C₁ -C₃alkylsulfonyl group or a C₁ -C₃ alkoxycarbonyl group; R⁴ is hydrogenatom; and X is CR² or N.
 2. An oxadiazolinone derivative according toclaim 1, wherein R¹ is a C₁ -C₃ haloalkyl group; R² is a halogen atom ornitro group; R³ is a C₁ -C₅ alkyl group, which alkyl group may besubstituted with a halogen atom, a C₁ -C₃ alkoxy group, a C₁ -C₃alkylthio group, a C₁ -C₃ alkylsulfinyl group or a C₁ -C₃ alkylsulfonylgroup; and X is CR².
 3. An oxadiazolinone derivative according to claim2, wherein R¹ is trifluoromethyl group; and R³ is a C₁ -C₅ alkyl group,which alkyl group may be substituted with an alkoxy group, a C₁ -C₃alkylthio group, a C₁ -C₃ alkylsulfinyl group or a C₁ -C₃ alkylsulfonylgroup.
 4. An oxadiazolinone derivative according to claim 3, wherein R³is a C₁ -C₅ alkyl group, which alkyl group may be substituted with a C₁-C₅ alkylthio group or a C₁ -C₃ alkylsulfonyl group.
 5. Anoxadiazolinone derivative according to claim 4, which is5-(1-methylthio-l-methylethyl)-3-(2-chloro-6-fluoro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.6. An oxadiazolinone derivative according to claim 4, which is5-(1,1-dimethylethyl)-3-(6-chloro-2-nitro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.7. An oxadiazolinone derivative according to claim 4, which is5-(1-methylthio-1-methylethyl)-3-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.8. An oxadiazolinone derivative according to claim 4, which is5-(1-methylsulfonyl-1-methylethyl)-3-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-2-one.9. An insecticidal composition which comprises an insecticidallyeffective amount of the oxadiazolinone derivative according to claim 1and an inert carrier.
 10. A method for controlling insect pests whichcomprises applying an insecticidally effective amount of theoxadiazolinone derivative according to claim 1 to the insect pests.